Metal-clad laminate adapted for printed circuits

ABSTRACT

A metallized, laminated substrate well adapted for the production of printed circuits is comprised of: 
     (A) an electrically insulating support element which comprises (a) a central core member comprising a major proportion by weight of a cellulosic or mica filler and a minor proportion by weight of a thermosetting resin, and (b) and (b&#39;) a pair of skin laminae coextensively secured to each face surface, respectively, of said central core (a), each of said skin laminae comprising a fibrous glass, asbestos or heat-stable synthetic polymer reinforcing filler, and a thermosetting resin impregnant, which thermosetting resin may either be the same as or different from the thermosetting resin comprising said central core member (a); and 
     (B) an electrically conducting metal foil (c) coextensively adhered to the exposed face surface of one or the other of said skin laminae (b) or (b&#39;).

This application is a division of application Ser. No. 314,014, filedOct. 22, 1981, now U.S. Pat. No. 4,456,657.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to substrates comprised of a reinforcedpolymeric material overcoated with metal, and, more especially, to suchsubstrates adapted for producing printed circuits. The topic metallizedsubstrates are typically generically designated as "metal-clad".

2. Description of the Prior Art

Such metallized substrates are well known to those skilled in this art(compare U.S. Pat. No. 4,110,147). They generally comprise anelectrically insulating support material and a conducting metal foiladhering to one or both of its face surfaces. This metal foil can be, inparticular, a copper, aluminum, nickel or stainless steel foil having athickness of between 10 and 100μ, depending upon the type of printedcircuit desired to be produced.

The metallized substrates in question can be rigid, semi-rigid orflexible, depending upon the composition of the insulating supportmaterial. The expression "semi-rigid substrate" designates a materialwhich can withstand elastic deformation, by bending, down to a verysmall radius of curvature.

In the case of the rigid or semi-rigid metallized substrates, to whichthe present invention relates more particularly, the insulating supportmaterial is typically formed by stacking together a certain number ofprepregs which each result from the association, known per se, of areinforcing filler of elongate structure with a polymeric material. Inthe case of a common reinforcing filler, such as, for example, a glassfabric weighing 200 g/m², an average of about 12 prepregs are used. Theusual prepregs are comprised of cellulose papers, cotton fabrics orglass fabrics impregnated with synthetic polymers. Phenol/formaldehyderesins, polyester resins and especially polyepoxy resins are theproducts most frequently employed. The reinforcing filler, namely, paperor glass fabric, is generally impregnated with a solution of polymer inan appropriate solvent, and this enables the polymeric binder topenetrate thoroughly between the fibers of the filler. The impregnatedstructure is then passed through an oven heated to a temperature whichenables the solvent to evaporate therefrom.

The manufacture of the metallized substrates consists of placing thestack of prepregs, covered with a metal foil on one or both of its facesurfaces, depending upon whether it is desired to obtain amonometallized or bimetallized substrate, between the platens of apress. The stack is then compressed at a temperature which permits theassociation or consolidation of the various constituents. In certaincases, it is necessary to use an adhesive in order for the metal foilsto adhere permanently to the prepregs.

SUMMARY OF THE INVENTION

In view of the fact that the demand for metallized substrates forprinted circuits is ever increasing, it is a major object of the presentinvention to provide for the increased manufacturing output thereof, byreducing the number of individual elements, in particular the number ofprepregs, from which same are fabricated. This simplification at themanufacturing level consistent with this invention is also accomplishedwithout detracting from the mechanical and electrical properties of theresultant substrates under the influence of heat.

Another object according to the present invention is to providemetallized substrates, the manufacture of which does not give rise toenvironmental pollution. As indicated hereinabove, the preparation ofthe insulating support material typically entails a process in which aseries of reinforcing structures are impregnated with a solution ofpolymer in an appropriate solvent. In order to obtain a prepreg whichcan be used for the remainder of the operations, the solvent must beremoved by drying. This solvent removal, despite all precautions whichmay be taken to recover same, is frequently a cause or source ofpollution. Other additional disadvantages related to the use of solventare, on the one hand, its purchase price, and, on the other hand, thelarge amount of energy required for drying. The reduction in the numberof prepregs as above outlined for purposes of simplifying themanufacture of the subject metallized substrates, therefore, is onemeans to solve this pollution problem. Another object of the presentinvention is to solve this problem completely, by dispensing with thecollodion method for preparing the remaining prepregs.

Yet another object of the invention is to provide metallized substratesfor printed circuits, which can easily be pierced by simple punching,and the internal composition of which enables, by applying thissimplified piercing technique, obtaining smooth-walled holes for thepassage therethrough of the electrical connections between the two facesurfaces.

Other objects and advantages of the present invention will become moreapparent from the description which follows.

Briefly, it has now been found that the above and other objects of theinvention are attained by providing a metallized substrate characterizedin that it comprises:

(A) an electrically insulating support material comprising three layers,namely:

(i) a central core (a) formed by the consolidation of:

(1) a major proportion by weight of a filler fabricated from either acellulosic material or from mica shavings, flakes or splits, with

(2) a minor proportion of a resin prepared from a thermosettingpolymeric material, and

(ii) two skins (b) and (b') disposed on either side of the central core(a) and formed by the consolidation of:

(3) a reinforcing filler fabricated from either a woven fabric or anon-woven fabric (in particular, mats and felts) of glass fibers,asbestos fibers or heat-stable synthetic polymer fibers, such as, forexample, polyamide-imide fibers or aromatic polyamide fibers, with

(4) a resin fabricated from a thermosetting polymeric material, which isidentical to or different from the resin (2) comprising said centralcore (a); and

(B) an electrically conducting metal foil (c) located against theexposed face surface of one or the other of the skins (b) and (b') (theother face surface of the said skin being in contact with said centralcore).

By the expression "cellulosic material" there is intended paper in theform of a pulp or strip, or woven fabrics, knitted fabrics or layers offibers shaped from natural cellulose or chemically modified cellulose.

DETAILED DESCRIPTION OF THE INVENTION

More particularly according to this invention, the mica flakes or splitsutilized are products which are usually commercially available. Thesesplits can be employed in the crude form, but in certain cases, in orderto improve the bond between the mica and the resin, it is advantageousto subject them to appropriate surface treatment, per se known to theart.

According to one preferred embodiment of the invention, the metallizedsubstrates as described above also possess a second metal foil (c')disposed against the free face surface, which has not yet beenmetallized, of the second skin (b') or (b).

The various layers (a) (b) (b') (c) or (a) (b) (b') (c) (c') arepermanently bonded to one another either by chemical bonding or adhesivebonding.

The central core (a) has a weight which advantageously constitutes 50 to95% of the weight of the metallized substrate. Its essential function isto serve as a filler for the metallized substrate, such as to providesame with the required thickness, which is generally between 1 and 3 mm.The substrates most frequently employed have a thickness of 1.5 to 1.6mm.

The essential functions of the two skins (b) and (b') are, on the onehand, to ensure the rigidity of the metallized substrate, and, on theother hand, to define an adhesive layer for the metal foils (c) and(c'). The total thickness of the two skins (b) and (b') in themetallized substrate ranges from about 0.01 to 0.3 mm.

In the central core (a), the proportion by weight of cellulosic materialor of mica splits, relative to the filler+resin together, typicallyranges from 60% to 95% and preferably from 65 to 90%.

The resin, which is a constituent of the central core (a) and also ofthe skins (b) and (b'), is comprised of a thermosetting polymericmaterial. Suitable resins which are exemplary are: phenolic resins, suchas, for example, condensation products of phenol, resorcinol, cresol orxylenol with formaldehyde or furfural; unsaturated polyester resins,prepared, for example, by reacting an unsaturated dicarboxylic acidanhydride with a polyalkylene glycol; epoxy resins, such as, forexample, the reaction products of epichlorhydrin with bisphenol A; andpolyimide resins, such as, for example, those obtained by reacting anunsaturated dicarboxylic acid N,N'-bis-imide with a primary polyamineand, if appropriate, with a suitable adjuvant.

As indicated above, the resin forming part of the central core (a) canbe identical to or different from that which comprises the skins (b) and(b').

The resin can be in the form of a thermosetting prepolymer (which has asoftening point and is still soluble in certain solvents) for anintermediate stage of production of the metallized substrate, or in thecompletely cross-linked form (which is infusible and totally insoluble)in the finished component, as it is normally used.

Preferably, the resin comprising the central core (a) is of the sametype as that which comprises the skins (b) and (b'), and it consists ofa polyimide resin obtained by reacting an unsaturated dicarboxylic acidN,N'-bis-imide with a primary polyamine in accordance with the detailsset forth in U.S. Pat. Nos. 3,562,223 and 3,658,764 and in U.S. Pat. Re.No. 29,316, the disclosures of which are hereby expressly incorporatedby reference. The polyimide resin can also be obtained by reacting thebis-imide with the polyamine and with various adjuvants, such as, forexample, mono-imides (according to U.S. Pat. No. 3,717,615), monomers,other than imides, containing one or more polymerizable groups of thetype CH₂ ═C< (according to U.S. Pat. No. 4,035,345), unsaturatedpolyesters (according to U.S. Pat. No. 3,712,933) or hydroxylatedorganosilicon compounds (according to U.S. Pat. No. 4,238,591), thedisclosures of which also being expressly incorporated by reference. Inthe case where such adjuvants indeed are used, it should be appreciatedthat the polyimide resin can be obtained either by directly heating thethree reactants (bis-imide, polyamine and adjuvant) together, or byheating the reaction product, or a mixture, of the adjuvant and aprepolymer, prepared beforehand, of bis-imide and polyamine.

In the following text, the expression "thermosetting prepolymer", whenit refers to the preferred polyimides, is to be understood as connotinga polymeric material which has a softening point and is still soluble incertain solvents and which can be: either the reaction product of abis-imide and a polyamine; or the reaction product of a bis-imide, apolyamine and an adjuvant; or the reaction product of a prepolymer ofbis-imide and polyamine, and an adjuvant; or also a mixture of aprepolymer of bis-imide and polyamine, and an adjuvant.

Even more preferably, the polyimide resin used in the present inventionis prepared by reacting a bis-maleimide, such asN,N'-4,4'-diphenylmethane-bis-maleimide, with a primary diamine, such as4,4'-diaminodiphenylmethane, and, if appropriate, with one of thevarious adjuvants mentioned above.

It should be appreciated that the polyimide resin comprising the centralcore (a) can, if appropriate, have a chemical composition which isidentical to or different from that of the polyimide resin comprisingthe skins (b) and (b'). Thus, if the central core (a) includes a fillerof a cellulosic material, it is very especially preferred that thepolyimide resin comprising the said central core preferably be apolyimide resin originating from the reaction of the bis-imide with thepolyamine and with one of the above-mentioned adjuvants, in particular ahydroxylated organosilicon compound. As regards the polyimide resincomprising the skins (b) and (b'), it can then have the same chemicalcomposition or can simply result from the reaction of the bis-imide withthe polyamine.

Examples of suitable hydroxylated organosilicon compounds areα,ω-dihydroxy-methylphenylpolysiloxane oils having from 4 to 9% byweight of hydroxyl groups.

As regards the skins (b) and (b'), the proportion by weight ofreinforcing filler, relative to the reinforcing filler+resin together,typically ranges from 20% to 90% and preferably ranges from 40 to 70%.

The metal foil or foils employed have all of the characteristics knownto those skilled in the art and referred to above. It is preferred touse copper foils having a thickness ranging from 15 to 70μ. The mostcommon thickness is 35μ.

The present invention also relates to a technique for the manufacture ofmetallized substrates of the above type.

This technique essentially comprises successively stacking together:

(i) a metal foil;

(ii) a first prepreg comprising a woven fabric or a non-woven fabric ofglass fibers, asbestos fibers or heat-stable synthetic polymer fibers,impregnated with a thermosetting prepolymer;

(iii) a felt or a composite comprising a cellulosic material or micasplits and a thermosetting prepolymer; and

(iv) a second prepreg as defined under (ii),

and then in compressing the stack at a temperature which permits theconsolidation of the various elements. This provides a substratemetallized on only one face surface.

According to another embodiment of the invention, a second metal foil(v) can be added to the layer (iv) of the stack, such as to provide asubstrate metallized on both face surfaces.

As indicated above, the skins (b) and (b') are formed by the associationof a reinforcing filler with a resin. More precisely, this associationis an impregnation. The impregnation of the filler can be carried out,in a conventional manner, by a collodion method, namely, by means of asolution of a thermosetting prepolymer in a suitable solvent, forexample, a polar solvent such as dimethylformamide, N-methylpyrrolidone,dimethylacetamide, diethylformamide or N-acetylpyrrolidone. However, inorder to dispense with the use of solvent and to completely solve thepollution problem referred to above, it is possible to impregnate thefiller under dry conditions by dusting it with the thermosettingprepolymer or by means of an aqueous dispersion of prepolymer; if apolyimide prepolymer is involved, the various techniques described inU.S. Pat. No. 4,038,450 and in British Pat. No. 1,400,512 can befollowed. These processes lead to the preparation of the prepregs (ii)and (iv) formed by a reinforcing filler and a prepolymer. During thesubsequent treatments (compression and heating of the stack referred toabove), these prepregs are converted to the skins (b) and (b') bycross-linking of the prepolymer.

The material which is converted, during the said subsequent treatments,to a central core (a) (or precursor material of the central core) is afelt or a composite comprised of a cellulosic material or mica and athermosetting prepolymer. The felt is produced by a papermaking methodand the composite is produced by a dry method.

According to the papermaking method, all of the ingredients, namely, atone and the same time the water, the filler (cellulosic material ormica) and the binder (thermosetting prepolymer) in powder form, areincorporated directly into a mixer referred to in the papermakingindustry as a "beater". The felt is then formed on a paper machine fromthe pulp obtained, and the water is extracted from the felt, on the onehand by draining and applying a vacuum, and on the other hand by dryingat a temperature on the order of 70° to 10° C., generally by passing thefelt through a ventilated oven. In this felt, the binder is still at theprepolymer stage. The felt prepared in this way has a density of between0.3 and 2, whereas, at the final stage, namely, after compression of thefelt and curing of the prepolymer, the density of the central coreranges from about 1.5 to 2.7.

It will be appreciated that the proportions by weight of the filler (forthe felt or the composite) of the reinforcing filler (for the prepregs)and of the thermosetting prepolymer which are used for the fabricationof the constituents (ii), (iii) and (iv) correspond to those indicatedhereinabove concerning the definition of the central core (a) and theskins (b) and (b'). It will also be appreciated that the constituent(iii) which is the precursor of the central core (a) must have a weightwhich generally represents 50 to 95% of the weight of the finalmetallized substrate.

According to the dry method, the filler and the thermosetting prepolymerare simply mixed under dry conditions to provide a pulverulentcomposite. The composite thus obtained is either directly molded withthe prepregs (ii) and (iv) and one or both of the metal foils (i) and(v), or, preferably, is subjected beforehand to a preliminary sinteringoperation in order to make it easier to handle for the purpose ofpreparing the metallized substrate.

According to the dry method, if the filler is mica, it is veryespecially preferred to use mica splits which have been subjected to asurface treatment beforehand. This treatment consists, in particular, incoating the mica splits with an alkoxysilane containing one or moreethylenically unsaturated groups, the amount of treating agent generallyrepresenting 0.1 to 3% of the weight of the micaceous filler. Examplesof suitable alkoxysilanes are vinyltriethoxysilane,methylvinyldiethoxysilane and vinyl-tris-(methoxyethoxy)-silane.

To produce the metallized substrates according to the invention, theconstituents (i), (ii), (iii), (iv) and, if appropriate (v), definedabove, are placed on a platen of a press. The assembly is then stronglycompressed. More precisely, the assembly is compressed, typicallybetween 10 and 300 bars, at a temperature which enables the prepolymerpresent in the various constituents to soften.

In the case of the preferred polyimide prepolymers obtained from abis-imide, a polyamine and, if appropriate, one of the above-mentionedadjuvants (generally having a softening point between 50° and 200° C.),the compression temperature is advantageously between 70° and 280° C.Preferably, in order to permit effective bonding (or joining) of thevarious constituents, the temperature is above 150° C.

These compression temperature conditions also apply to the other type ofthermosetting prepolymers falling within the scope of the presentinvention. In general, heating the prepolymers makes it possible tosuccessively soften and then cure them. It is of course possible to bakethe assembly, for example, for a few hours at 200° C. or above.

The aforesaid technique for the manufacture of the metallized substratesaccording to the invention has numerous advantages.

As has already been mentioned, this manufacture is simplified by virtueof using a restricted number of constituents, and it makes it possibleto wholly or partially dispense with processes for impregnating areinforcing structure by a collodion method, which processes causepollution.

However, there are other advantages. The preparation of the precursor ofthe central core (a) by a papermaking method (felt) is a high-efficiencyprocess. Furthermore, the papermaking method makes it possible torecycle the waste; there is no disadvantage in re-introducing, into thebeater, the felt waste formed before drying. Likewise, the dry method(composite), which proceeds via a sintered preform, also eliminates theexistence of waste. Furthermore, it is noted that there is virtually noflow of polyimide during the final hot compression. In brief, thispossibility of recycling, together with virtually zero flow duringcompression, ensures a very small loss of resin during manufacture.

The quality of the characteristics of the metallized substratesaccording to the present invention (in particular: mechanicalcharacteristics; peel strength of the metal foils; heat resistance;water resistance; and electrical characteristics) is totallysatisfactory and compatible for use in the electronics industry

In order to further illustrate the present invention and the advantagesthereof, the following specific examples are given, it being understoodthat same are intended only as illustrative and in nowise limitative.

EXAMPLE 1

In this example, a detailed description is given of the technique forthe manufacture of a bicoppered substrate (also referred to as acopper-clad) comprising a central core made from a paper felt,sandwiched between two skins made from an impregnated glass fabric.

(1) Production of the paper felt:

The following ingredients were charged into the mixer (referred to asthe beater) of a paper machine:

(i) an unbleached kraft-type paper pulp consisting of 276 g ofcellulosic material dispersed in 8 liters of water;

(ii) 83 g of a powder of a prepolymer prepared fromN,N'-4,4'-diphenylmethane-bis-maleimide and 4 4'-diaminodiphenylmethane(molar ratio bis-imide/diamine=2.5) and having a softening point of 70°C.;

(iii) 35.5 g of α,ω-dihydroxy-methylphenylpolysiloxane oil containing 7%by weight of hydroxyl groups; and

(iv) 15.1 g of an aqueous solution containing: 1.5 g of polyvinylalcohol (Rhodoviol 20/140 from RHONE-POULENC), 1.8 g of propylene glycoland 0.09 g of sorbic acid.

Polyvinyl alcohol, propylene glycol and sorbic acid are well-knowningredients in the various processes for the preparation of papers.

The entire mass was homogenized by agitation for about 1 hour. In orderto facilitate malaxation, the pulp was diluted by adding a small amountof water (about 3 liters).

After malaxation, the pulp was introduced in portions of about 2,800 ginto a paper machine of the following type: a "Franckformer" equippedwith a square-shaped grid having a side length of 300 mm, with a squaremesh having a side length of 120μ. The water was removed each time bynatural draining and by applying a vacuum (pressure reduced to 50 mm ofmercury). The various felts obtained were dried at 90°-100° C. for twohours in a ventilated oven. These felts had dimensions of about300×300×10 mm and each weighed between 110 g and 140 g. Same comprisedabout 70% by weight of cellulosic fibers and 30% by weight of polyimideprepolymer (bis-imide/diamine prepolymer+organosilicon compound). Theother components, namely, polyvinyl alcohol, propylene glycol and sorbicacid, being soluble in water, were totally eliminated in the aqueousphase, which was recycled.

(2) Production of the impregnated glass fabric:

A collodion was prepared which comprised 50% by weight ofN-methylpyrrolidone and 50% by weight of a polyimide prepolymer preparedfrom N,N'-4,4'-diphenylmethane-bis-maleimide and4,4'-diaminodiphenylmethane (molar ratio bis-imide/diamine=2.5) andwhich had a softening point of 100° C.

This collodion was deposited with a paint brush on both face surfaces ofa glass fabric of the Tissaverre 278 type (cloth weighing 200 g/m ), soas to have a weight ratio glass fabric/polyimide prepolymer of 65/35.The collodion was deposited in two stages separated by drying for 1minute at 140° C. After the second application drying was carried outfor 10 minutes at 140° C. in a ventilated oven. Two pieces having thefollowing dimensions: 300×300×0.25 mm, and each weighing 27.5 to 28 g,were cut out of the web of prepreg; these were intended to form the twosupports enclosing the paper felt.

(3) Production of the copper-clad:

The following lamina were successively stacked on the platen of a press:

(i) a first 35μ thick copper foil of the TC Foil type, having a squareshape with a side length of 300 mm;

(ii) one of the prepregs;

(iii) a felt weighing 124 g;

(iv) the second prepreg; and

(v) a second 35μ copper foil, and the assembly was then compressed:

for 15 minutes at 160° C. under 25 bars (with degassing in the 3rd and5th minute),

and then for 2 hours at 180° C. under 25 bars (the temperature of 180°C. being set after the 15 minutes without interrupting the cycle).

There was no flow of pure resin.

This provided a 300×300×1.6 mm copper-clad weighing 237 g. In thisarticle, the weight of the central core was about 52% of the totalweight of the copper-clad.

The mechanical flexural strength properties of the copper-clad were asfollows (measurements according to ASTM Standard Specification D 790):

(a) flexural strength at about 20° C.: 34.5 kg/mm²,

(b) flexural modulus at about 20° C.: 1,900 kg/mm².

(c) The peel strengths of the copper were as follows: (the peeling wascarried out, perpendicular to the bonding plane, on a 1 cm wide strip ofcopper-clad):

    ______________________________________                                                     After      After     After                                                    250 hours  500 hours 1,000 hours                                        Time 0                                                                              at 150° C.                                                                        at 150° C.                                                                       at 150° C.                           ______________________________________                                        Averages in                                                                            1.77    1.85       1.87    1.92                                      kg/cm                                                                         ______________________________________                                    

The peel strengths were very homogeneous and the heat aging was overallfavorable.

EXAMPLE 2

In this example, a detailed description is given of the technique forthe manufacture of a copper-clad comprising a central core made from amica felt, sandwiched between two skins made from an impregnated glassfabric.

(1) Production of the mica felt:

The following ingredients were charged into the mixer (referred to asthe "beater") of a paper machine:

(i) 63.8 g of mica splits of the Suzorite 60 S type;

(ii) 11.2 g of polyimide prepolymer prepared fromN,N'-4,4'-diphenylmethane-bis-maleimide and 4,4'-diaminodiphenyl-methane (molar ratio bis-imide/diamine=2.5) and having a softening pointof 70°; and

(iii) 0.5 liter of water.

The entire mass was homogenized by agitation for 10 minutes and thenintroduced into the Franck paper machine, this time equipped with adisc-shaped grid having a diameter of 200 mm, with a square mesh havinga side length of 120μ. The circular felt obtained was dried at 100° C.for 2 hours in a ventilated oven. It had a thickness of about 2.5 mm andweighed 71 g. It about 85% by weight of mica and 15% by weight ofpolyimide prepolymer. For the remainder of the operations, a square(inscribed) of felt having a side length of 140 mm and weighing 45 g wascut out of this circular felt of diameter 200 mm.

(2) Production of the impregnated glass fabric:

Reference should be made to Example 1, part (2). It should be noted thattwo square prepregs having a side length of 140 mm were cut out of theweb obtained.

(3) Production of the copper-clad:

The procedure indicated above in Example 1 was followed, but two 35μthick, square copper foils having a side lengths of 140 mm were used.

The compression conditions were as follows:

15 minutes at 160° C. under 40 bars (with degassing in the 3rd and 5thminute);

and then 1 hour at 180° C. under 40 bars (the temperature of 180° C.being set after the 15 minutes without interrupting the cycle).

There was no flow of pure resin.

The shaped article obtained was then baked for 24 hours at 200° C.

The characteristics of the copper-clad were as follows:

dimensions: 140×140×1.6 mm; weight: 69.8 g; the weight of the centralcore corresponding to about 64% of the total weight of the copper-clad.

flexural strength: at about 20° C.: 20.7 kg/mm², at 180° C.: 18.4kg/mm².

flexural modulus: at about 20° C.: 3,250 kg/mm², at 180° C.: 2,755kg/mm².

peel strength (time 0): 1.6 kg/cm (average value)

coefficient of expansion: 10×10⁻⁶ cm/cm/°C.

EXAMPLE 3

In this example, a detailed description is given of the technique forthe manufacture of a copper-clad comprising a central core made from asintered mica composite, sandwiched between two skins made from animpregnated glass fabric.

(1) Production of the sintered composite:

The following ingredients were dry-mixed in an industrial CNTA-typemixer:

(i) 85 parts by weight of mica splits of the Muscovite Adriss 16 meshtype, treated with 1% of vinyltriethoxysilane (the treatment typicallyconsisted of mixing the filler with the silane and then leaving themixture obtained to stand in contact with air for about 3 days), and

(ii) 15 parts by weight of polyimide prepolymer prepared fromN,N'-4,4'-diphenylmethane-bis-maleimide and 4,4'-diaminodiphenylmethane(molar ratio bis-imide/diamine=2.5) and having a softening point of 70°C.

The duration of this mixing operation was about 5 minutes.

80 g of the pulverulent composite thus obtained were then introducedinto a 220×120×20 mm mold (between two aluminum sheets in order tofacilitate the subsequent release of the molding), the mold and itscontents were then heated to a temperature of 120° C. and a pressure of200 bars was applied for 5 minutes. The molded shaped article was thenreleased hot. The sintered molding obtained weighed 80 g. It comprisedabout 85% by weight of mica and 15% by weight of polyimide prepolymer.

(2) Production of the impregnated glass fabric:

The procedure indicated in Example 1, part (2) was followed. It shouldbe noted that two 220×120 mm rectangular prepregs were cut out of theresultant web.

(3) Production of the copper-clad:

35μ thick, 220×120 mm copper foils were used.

The following elements were successively stacked on the platen of apress: the first copper foil, one of the prepregs, the sintered molding,the second prepreg and the second copper foil, and the assembly was thencompressed for 45 minutes at 250° C. under 200 bars. There was no flowof pure resin. The article obtained was then baked for 24 hours at 200°C.

The characteristics of the copper-clad were as follows:

dimensions: 220×120×1.6 mm; weight: 107 g; the weight of the centralcore corresponded to about 75% of the total weight of the copper-clad.

flexural strength: at about 20° C.: 22.5 kg/mm², at 200° C.: 17.8kg/mm², at 250° C.: 14.5 kg/mm².

flexural modulus: at about 20° C.: 2,285 kg/mm², at 200° C.: 1,905kg/mm², at 250° C.: 1,660 kg/mm².

peel strengths:

    ______________________________________                                                     After      After     After                                                    141 hours  500 hours 1,000 hours                                        Time 0                                                                              at 200° C.                                                                        at 200° C.                                                                       at 200° C.                           ______________________________________                                        Averages in                                                                            1.82    1.93       1.67    1.93                                      kg/cm                                                                         ______________________________________                                    

weight variation (in %, relative to the initial weight) during the agingat 200° C.: after 141 hours: ΔW=-0.1% after 1,000 hours: ΔW=-1.5%.

test for water uptake after 24 hours (weight variation in %, relative tothe initial weight): in steam: ΔW=+0.38% immersion in boiling water:ΔW=+0.74%.

electrical characteristics:

    ______________________________________                                                                   After 24 hours                                     Properties measured                                                                           Initial values                                                                           in water                                           ______________________________________                                        Dielectric strength                                                                            23         13                                                in KV/mm                                                                      Permittivity ε at 1 MHz                                                               3.6        3.9                                                Tangent of the loss                                                                           8.4 × 10.sup.-3                                                                    50 × 10.sup.-3                               angle at 1 MHz                                                                Resistance in Ω × cm                                                              12 × 10.sup.14                                                                     2.5 × 10.sup.14                              ______________________________________                                    

coefficient of expansion: 10×10⁻⁶ cm/cm/°C.

While the invention has been described in terms of various preferredembodiments, the skilled artisan will appreciate that variousmodifications, substitutions, omissions, and changes may be made withoutdeparting from the spirit thereof. Accordingly, it is intended that thescope of the present invention be limited solely by the scope of thefollowing claims.

What is claimed is:
 1. A process for the manufacture of a metallizedsubstrate comprising successively stacking: (i) an electricallyconducting metal foil; (ii) a first skin laminae; (iii) a core member;and (iv) a second skin laminae; and thence compressing said stack undersubstrate consolidating temperatures, said core member (iii) comprisinga major proportion by weight of a cellulosic or mica filler and aproportion of less than 40% by weight of a thermosetting resin which isa polyimide resin or a mixture of polyimide resin and epoxy resin, saidcentral core (iii) being prepared by papermaking technique, and skinlaminae (ii) and (iv) each consisting of a fibrous glass, asbestos orheat-stable synthetic polymer reinforcing filler, and a thermosettingresin impregnant, which thermosetting resin may either be the same ordifferent from the thermosetting resin comprising said core member(iii).
 2. The process as defined by claim 1, wherein said metal foil (i)is a copper foil.
 3. The process as defined by claim 1, wherein saidcompression is carried out at a pressure ranging from 10 to 300 bars andunder a temperature ranging from 70° to 280° C.
 4. The process asdefined by claim 1, wherein the core member (iii) comprises 50 to 95% ofthe weight of the overall metallized substrate.
 5. The process asdefined by claim 1, the filler which comprises said core member (iii)comprising mica splits.
 6. The process as defined by claim 1, wherein inthe core member (iii), the proportion by weight of cellulosic or micafiller, relative to the combined weight filler+resin, ranges from 60% to95%.
 7. The process as defined by claim 1, wherein in the skin laminae(ii) and (iv), the proportion by weight of reinforcing filler, relativeto the combined weight reinforcing filler+resin, ranges from 20% to 90%.8. The process as defined by claim 1, wherein an electrically conductingmetal foil (v) is added to the stack after second skin laminae (iv)before compression of said stock under substrate consolidatingtemperatures.
 9. The process as defined by claim 8, wherein each of saidmetal foils (i) and (v) is a copper foil.
 10. The process as defined byclaim 1, wherein said resin comprising said skin laminae (ii) and (iv)is a phenolic, unsaturated polyester, epoxy, or polyimide resin.
 11. Theprocess as defined by claim 10, wherein said resin comprises athermosetting prepolymer.
 12. The process as defined by claim 11,wherein said resin comprising said core member (iii) is of the same typeas that comprising said skin laminae (ii) and (iv), and is a polyimideresin prepared by reacting an unsaturated dicarboxylic acidN,N'-bis-imide with a primary polyamine.
 13. The process as defined byclaim 12, said polyimide resin being prepared by reacting an unsaturateddicarboxylic acid N,N'-bis-imide, a primary polyamine, and a comonomerselected from the group consisting of a mono-imide, a monomer comprisingat least one CH₂ ═C< function, an unsaturated polyester, and ahydroxylated organosilicon compound.
 14. The process as defined by claim13, said core member (iii) comprising a cellulosic filler, and saidpolyimide resin being prepared by reacting an unsaturated dicarboxylicacid N,N'-bis-imide with a primary polyamide and with a hydroxylatedorganosilicon compound.